10.

3 Two Component System

10.3.1 Ideal Solution
When a system contains more than one component, interaction
between the two may result in different changes.
In a system that consists of 2 components that do not react with each
other...
 One component is considered to be the SOLUTE

 And the other the SOLVENT.
A two component system may result in a homogeneous mixture or a
heterogeneous mixture.
Heterogeneous mixtures form when the solute and the solution is
immiscible.
A few examples of a 2-component heterogeneous mixture would be:

  H2O + Benzene (liquid – liquid)

 NaCl + Benzene (solid – liquid)
In a homogeneous system, the two components that mix would be
miscible…

Solution = Liquid + Solid

Example:
Glucose(s) + Water = Glucose solution

Solution = Liquid + Gas

Example:
O2(g) + Water = Disollved O2 in water

Solution = Liquid + Liquid

Example:
Alchohol + Water = Alchohol solution

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 In a homogeneous 2-component mixture, interaction between the
components would complicate the study of analysis of the change in
phases of the system.
In order to simplify things, we may have to create a simplistic model
(very much like Ideal Gas for gas studies)…
An IDEAL SOLUTION is a solution in which…
 the forces of attractions of all components: solute-solute, solute-
 solvent, and solvent-solvent are all identical.
 when solution is formed with no evolution or absorption of heat
 (∆H) occurs
 solution obey Raoult’s law.

RAOULT’S LAW
The saturated partial vapour pressure of each component over
a solution, PA, is equal to the product of the mole fraction of
that component in the solution, χA and the saturated vapour
pressure of that component when pure, PAo.

χ o
for dilute solution and at constant
PA = A PA temperature
Where…

o
and PA = vapour pressure of pure
component A under same

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As such, the total vapour pressure of the system would then be…

PT = PA + PB
χ o χ o
PT = A PA + B PB

Exercise 4
o 4
At 80 C, the vapour pressure for Benzene is 10.0 x 10 Pa and the
4
vapour pressure for Toluene is 4.0 x 10 Pa. If 7.8 g of benzene forms
an ideal solution with 36.8 g toluene, determine...
a) The partial pressures of benzene and toluene
b) The total vapour pressure of the mixture of the solution
(Molar mass: Benzene = 78 g/mol , Toluene = 92 g/mol)

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 χ
Based on Raoult’s Law, a Vapour Pressure vs Mole Fraction (P vs )
diagram would look like this...

In a 2-component system, it is unlikely that both the components have

the same boiling point.
Since they have different boiling points, they would likewise have
different volatility.
As such the more volatile
component would logically
produce more vapours, and the
less volatile, less vapours.
This means that the
composition of their vapours
would not be the same as the
composition of the liquid
phases.

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The composition of the vapour pressure of an ideal 2-component
mixture of A & B can be represented by an additional curve below the
liquid composition line.

χ
For example, a mixture of 50% A & 50% B (i.e. A = 0.5)...
Would have a vapour composition of...
Since volatility is inversely proportional to boiling point, a pure
solution with high vapour pressure would mean that it has low boiling
point vice versa.
χ
As such the shape of the P vs diagram...
χ
Would almost mirror the shape of the Boiling Point vs diagram...

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Exercise 5
The phase diagram below shows the boiling point of an ideal A−B
mixture solution at various mole fractions. Use the diagram to
determine:
a) The boiling point of a solution of 30% A.
b) The mole ratio of A and B of the vapour of the solution
mentioned in (a).
T (OC)
110OC
VAPOUR
LIQUID

80OC

0 MOLE FRACTION OF A 1.00

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The Boiling-Point vs Mole Fraction phase diagram also tells that
simple distillation alone is not adequate to separate/purify one of two
components.
The example below tells that the vapour product is NOT pure A but
rather a solution with a higer composition of A!

In order to separate a 2-component

system completely into pure
components, we need to use the
fractional distillation process.
Fractional distillation is a
procedure for separating
components of a solution based on
their different boiling points.
When a solution containing 2
substances is boiled, the vapour
formed is richer in the more
volatile component.
As the vapour condenses and re-evaporates, the subsequent
composition of the vapour contains increasing amounts of the more
volatile component.
The final distillate would then contain the pure component of the
more volatile (lower boiling point) component.

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8
 10.3.2 Non-ideal Solution
Most solutions are non-ideal.
This is because it is almost impossible to find a 2-component solution
whereby the interactive forces between solute-solute, solute-solvent
and solvent-solvent is exactly the same.
Non-ideal solutions are considered to have “deviated” from Raoult’s
Law.
Therefore…
χ o χ o
PT ≠ A PA + B PB

There are two categories of non-ideal solutions:

 POSITIVE DEVIATION from Raoult’s law

 NEGATIVE DEVIATION from Raoult’s law

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a) Positive Deviation from Raoult’s Law

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 A MORE volatile mixture:
 The liquid molecules escape more easily into the gaseous
state and the vapour pressure is higher than that expected by
Raoult’s law
Longer distance between liquid molecules
 More empty space in the mixture: VT > VA + VB
Heat change, H = (positive value) (ENDOTHERMIC)

b) Negative Deviation from Raoult’s Law

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A LESS volatile mixture:
 It is more difficult for the liquid molecules to escape into the
gaseous state and the vapour pressure is lower than that
expected by Raoult’s law
Shorter distance between liquid molecules
 Less empty space in the mixture: VT < VA + VB
Heat change, H = (negative value) (EXOTHERMIC)

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c) Azeotropic Point
Due to the deviation to Raoult’s Law, the Temperature−Composition
χ
(T vs ) diagrams would form either a maximum (negative deviation)
or a minimum (positive deviation) point.

Solutions that are not azeotropic mixtures, when boiled, will produce
vapours with different composition from its solution.

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But azeotropic mixtures, when boiled, produce vapours with the
SAME composition with its solution.

Due to these characteristics, an azeotropic mixture cannot be

separated into its components simply by using the distillation method.

Exercise 6
The boiling points of trichloromethane and ethanol are 61.2 C and
78.5 C, respectively. They form an azeotropic mixture which has a
boiling point of 56.3 C and contains 7.0 % by mass of ethanol.
Sketch the Boiling Point−Composition phase diagram for this system.
Mark clearly the liquid and vapour curves on the diagram.

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Exercise 7
Based upon the Temperature-Composition phase diagram for ethanol-
ethyl acetate solution at 1 atmosphere, answer the following
questions.
i. Label the vapour and the liquid curve for the given phase
diagram.
ii. Determine the boiling point for the pure solution of ethanol and
ethyl acetate.
iii. What is the composition of the azeotrop mixture? State the
azeotropic boiling point.
iv. If a fractional distillation is done on a mixture of 4.00 mol
ethanol and 1.00 mol ethyl acetate, predict the first and second
distillate.

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36
EXERCISE
1. Define the following terms :
i. Phase
ii. Component

2. State the number of phases and components for each of the system given in the
table below :
System Number of Phases Number of Components
Mixture of O2, N2 and CO2 gases
Mixture of ethanol and water
Immiscible solution of benzene
and water
HNO3(aq) which is in an
equilibrium with its vapour

3. Substance X has its triple point at 18○C and 0.5 atm. The melting point and boiling
point are 20○C and 300○C respectively. Sketch the phase diagram for X.

4. Xenon is a noble gas. The melting point and boiling point for xenon are -112○C and
- 107○C respectively. The triple point of xenon is at -121○C and 282 torr whereas
the critical point is at 16.6○C with a pressure of 57.6 atm.
(a) Sketch and label a phase diagram for xenon.
(b) Compare the density of xenon in liquid and solid phases.

5. Figure below shows the phase diagram for water.

P

C A

•E •F

D
B •G
T

(a) Which curve represents the equilibrium of ice and water vapour?
(b) State the phase changes when
i) Pressure of a sample at point G is increased to E at constant temperature

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 ii) A sample at point E is heated at constant pressure until point F
is reached.
(c) Name the point which the BC line intersects with 1 atm line.

6. (a) Distinguish between the boiling point of a liquid and the normal boiling point of
a liquid.
(b) Explain using a phase diagram why the normal boiling point of water is increased
when a nonvolatile solute is added while the freezing point is decreased.

7. State Raoult’s law.

(a) At 300 K, pure ethanol has a vapour pressure of 22.40 kPa and the vapour pressure
for pure methylcyclohexene is 37.33 kPa. An solution X, which a mixture of these 2
components, has a vapour pressure of 50.22 kPa. If the mole fraction of ethanol in
the solution is 0.65, determine whether the X solution is ideal or not.

(b) According to your answer in (a), state whether the statements below are true or false
in explaining characteristics of a solution X.
i) the solution has a negative deviation.
ii) heat is released when both components are mixed.
iii) the volume increases during preparation of the solutions.
iv) the attractive forces between ethanol and water are greater than between
pure ethanol molecules or pure water molecules.

8. Pure benzene ( Mr = 78.1 ) has a vapour pressure of 121.8 torr, at 30○C. Dissolving
15.0 g of a nonvolatile solute in 250 g of benzene produced a solution having a vapour
pressure of 120.2 torr. Determine the molecular weight of the solute.

9. The vapour pressure of pure benzene is 100 torr, while that of pure ethyl alcohol is 44
torr at 25○C. Assuming ideal behaviour, calculate the vapour pressure of a solution
which contains 10.0 g of each substance at the same temperature.

10. The vapour pressures of pure benzene and pure toluene are 119.0 torr and 37.0
torr, respectively at 30○C.
(a) What is the composition of the vapour which is in equilibrium with a benzene-
toluene solution containing the following mole fraction of benzene.
i. 0.40
ii. 0.60
(b) Assuming ideal behaviour, plot a vapour pressure-composition diagram for the
solution. Include in the diagram the composition of vapour which is in equilibrium
with the solution.

11. (a) The vapour pressure of pure liquid solvent A is 0.08 atm. When a nonvolatile
substance B is added to the solvent, its vapour pressure drops to 0.06 atm. What is
the mole fraction of component B in the solution?
(b) The vapour pressure of pure water at 26○C is 25.21 torr. Calculate the vapour
pressure of a solution, which contains 20.0 g glucose, C6H12O6, in 70 g water.

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 (c) The vapour pressure of pure water at 25○C is 23.76 torr. If the vapour pressure
of a solution containing 5.40 g of a nonvolatile substance in 90.0g water is 23.32
torr, compute the molecular weight of the solute.

12. A mixture of 1,2-dibromoethene C2H4Br2, and 1,2-dibromopropane, C3H6Br2 form an

ideal solution. At 85○C the vapour pressure of these two pure liquids are 173 and 127
torr, respectively.
(a) If 10.0 g 1,2-dibromoethene is dissolved in 80.0 g of 1,2-dibromopropane, calculate
the partial pressure of each component and the total pressure of the solution at 85○C.

(b) Calculate the mole fraction of 1,2-dibromoethene in the vapour phase, which is
in equilibrium with the above solution.

13. The boiling point-composition phase diagram for a homogenous mixture of water and
M at a pressure of 1 atm is given below:
Boiling point
150
140
130
120
110
100

0 %M 100 mole fraction

(a) If the solution consist of 70% M and undergoes fractional distillation, what is the
i. boiling point of the mixture?
ii. composition of the vapour at this temperature?
iii. first distillation product?

(b) i) What is the composition of the first drop of distillate, if the vapour with a
liquid composition of 85% M at 140○C is condensed?
ii) Based on the graph, determine whether the solution is an ideal solution.

14. The boiling point of benzene is 80 ○C whereas that of ethanol’s is 78.5 ○C. The vapour
pressure when these two components are mixed is greater than the vapour pressure of
pure benzene and pure ethanol. An azeotropic mixture with a 32.4 % ethanol
composition is obtained.
(a) Sketch and label the boiling point-composition phase diagram for the mixture.
(b) Explain the shape of the curve with respect to the attractive forces between
molecules.
(c) Name the distillation product if a fractional distillation is carried out on the mixture
with a 50 % ethanol composition.

15. (a) When 10.6 g of nonvolatile substance is dissolved in 740 g of ether, its boiling point
is raised to 0.284○C. What is the molecular weight of the substance? (Kb ether
= 2.11○C m-1)
(b) A solution was made up by dissolving 3.75 g of a pure hydrocarbon in 95.0 g of
acetone. The boiling point of pure acetone was observed to be 55.95○C, and of the

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 solution, 56.50○C. If the molal boiling point constant of acetone, Kb acetone is
1.71○C m-1, what is the molecular weight of the hydrocarbon?

16. The boiling point-composition phase equilibrium diagram for HCl (aqueous) solution
is given below:
Boiling point

100
85

0 100
% HCl composition
Referring to the graph, what is the
i. boiling point of pure HCl?
ii. composition of the azeotropic mixture?
iii. type of deviation?
iv. first distillation product if the composition of HCl solution used in
distillation is 40 %?

17. The molecular weight of an organic compound is 58.0 g mol-1. Compute the boiling
point of a solution containing 24.0 g of the solute in 600 g of water, when the pressure
is such that water boils at 99.725○C. (Kb water = 0.513○C m-1)

18. A solution containing 3.50 g of solute X in 50.0 g of water has a volume of 52.5 mL and
a freezing point of –0.86○C. Calculate
i. the molality, mole fraction and molarity of X.
ii. the molecular weight of
X. (Kf X = 1.86○C m-1)

19. (a) The osmotic pressure of blood is 7.65 atm at 37○C. How much glucose should be
used per litre for an intravenous injection in order to obtain the same osmotic
pressure as blood?
(b) A solution of crab heamocyanin, a pigmented protein extracted from crabs, was
prepared by dissolving 0.750 g heamocynin in 125cm3 of an aqueous medium. At
4○C, an osmotic pressure rise of 2.6 mmHg of the solution was observed.
Determine the molecular weight of heamocynin.

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STPM Past Year Questions
Q5-P2-2004
b) The boiling point-composition phase diagram for the solution of
ethanol in water is shown below:
Boiling Point/oC

100

Vapour
78.3
Liquid
78.1

Azeotrope

0 Composition of Ethanol 96 100

i) Discuss the type of deviation from Raoult’s law for the above
solution.
ii) The alcoholic solution formed from the fermentation of
carbohydrates contains about 12% to 15% ethanol. Explain
why pure ethanol cannot be obtained from the alcoholic
solution by fractional distillation.

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Q1-P2-2000
The table below lists the temperature and pressure for the critical
point and triple point of a substance X.
o
Temperature ( C) Pressure (atm)
Critical Point 31 73
Triple Point −57 5
o
X sublimes at −78 C under atmospheric pressure. The freezing point
o
of X increases by 2 C for every 10 atm in pressure.
a) Based on the information given above, sketch the phase diagram
for X.
o
b) Calculate the freezing point of X, in C, under a pressure of
75 atm
c) Explain why the freezing point of X increases with pressure.
d) Solid X is known as dry ice.
(i) How can liquid X be obtained from dry ice?
(ii) State one industrial use for dry ice.

Q4-P2-1999
a) Glucose is completely miscible in water.
(i) Sketch a labelled vapour pressure-temperature diagram for
pure water and aqueous glucose on the same axis.
(ii) Based on the diagram you have sketched in (i), explain
quantitatively the effect on the vapour pressure and the
boiling point of water when glucose is dissolved in it.
(iii) Outline how you would separate aqueous glucose into its
components.

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b) Benzene and methylbenzene form a solution that obeys Raoult’s
law. The vapour pressures of pure benzene and pure
methylbenzene are 12.7 kPa, and 3.9 kPa respectively at 298K.
(i) State Raoult’s lae.
(ii) Draw and label, on a graph paper, the vapour pressure-
composition graph for a mixture of benzene and
methylbenzene.
(iii) Determine the vapour pressure of a solution containing 2.0
moles of benzene and 3.0 moles of methylbenzene.
(iv) Explain quantitatively how the vapour pressure of
methylbenzene is affected when benzene is dissolved in it.
(v) Describe how a mixture of benzene and methylbenzene can
be separated.

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